EP3038810A1 - Récipient et son procédé de fabrication - Google Patents

Récipient et son procédé de fabrication

Info

Publication number
EP3038810A1
EP3038810A1 EP14838960.4A EP14838960A EP3038810A1 EP 3038810 A1 EP3038810 A1 EP 3038810A1 EP 14838960 A EP14838960 A EP 14838960A EP 3038810 A1 EP3038810 A1 EP 3038810A1
Authority
EP
European Patent Office
Prior art keywords
layer
core
parison
hdpe
formulation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14838960.4A
Other languages
German (de)
English (en)
Other versions
EP3038810A4 (fr
Inventor
Jeffrey C. Minnette
David D. SUN
Phillip A. DRISKILL
Birju A. SURTI
Anthony R. GUARNERA
Jonathan K. Williams
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Berry Global Inc
Original Assignee
Berry Plastics Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Berry Plastics Corp filed Critical Berry Plastics Corp
Publication of EP3038810A1 publication Critical patent/EP3038810A1/fr
Publication of EP3038810A4 publication Critical patent/EP3038810A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/10—Extrusion moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/49—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42—Component parts, details or accessories; Auxiliary operations
    • B29C49/46—Component parts, details or accessories; Auxiliary operations characterised by using particular environment or blow fluids other than air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42—Component parts, details or accessories; Auxiliary operations
    • B29C49/46—Component parts, details or accessories; Auxiliary operations characterised by using particular environment or blow fluids other than air
    • B29C2049/4602—Blowing fluids
    • B29C2049/4605—Blowing fluids containing an inert gas, e.g. helium
    • B29C2049/4608—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42—Component parts, details or accessories; Auxiliary operations
    • B29C49/62—Venting means
    • B29C2049/622—Venting means for venting air between preform and cavity, e.g. using venting holes, gaps or patterned moulds
    • B29C2049/627—Venting means for venting air between preform and cavity, e.g. using venting holes, gaps or patterned moulds using vacuum means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/006—Using vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/007—Using fluid under pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3041—Preforms or parisons made of several components having components being extruded
    • B29C2949/3042—Preforms or parisons made of several components having components being extruded having two or more components being extruded
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42—Component parts, details or accessories; Auxiliary operations
    • B29C49/4252—Auxiliary operations prior to the blow-moulding operation not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42—Component parts, details or accessories; Auxiliary operations
    • B29C49/48—Moulds
    • B29C49/4802—Moulds with means for locally compressing part(s) of the parison in the main blowing cavity
    • B29C49/4817—Moulds with means for locally compressing part(s) of the parison in the main blowing cavity with means for closing off parison ends
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/065—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0063—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages

Definitions

  • the present disclosure relates to containers, and in particular to containers made from polymeric materials. More particularly, the present disclosure relates containers made using a blow-molding process.
  • a container is formed to include an interior region adapted to store products therein.
  • the container is made using a container-molding process in which a tube of polymeric materials is extruded and then blow molded.
  • a container-molding process is used to establish a multi-layer container from a multi-layer tube.
  • the container-molding process includes an extruding operation, a blow-molding operation, and a trimming operation.
  • a co-extrusion system co-extrudes a multi-layer tube that comprises an inner layer, an outer layer spaced apart from the inner layer, and a core layer located therebetween.
  • the core layer is made from relatively low-density insulative cellular non-aromatic polymeric materials.
  • the multi-layer tube is located in a mold and pressurized gas is pumped into a spaced formed in the multi-layer tube to cause the multi-layer tube to expand and take on a shape of the mold so that a vessel is established.
  • excess materials are removed from the vessel to establish the multi-layer container.
  • the multi-layer container includes an inner layer, an outer layer spaced apart from the inner layer, and a compressed core layer located therebetween.
  • the compressed core layer is made from relatively low-density insulative cellular non-aromatic polymeric material which has been compressed during the blow-molding operation.
  • the multi-layer container has a relatively low density while stack strength, rigidity, and top load performance are maximized.
  • the low density of the multi-layer container also minimizes an amount of polymeric material used to form the multi-layer container.
  • FIG. 1 is a diagrammatic and perspective view of a container-molding process in accordance with the present disclosure showing that the container-molding process includes an extruding operation in which a multi-layer tube is extruded from a co-extrusion system, a closing operation in which a mold is closed around the multi-layer tube, an inserting operation in which a blow needle is inserted into a tube space formed in the multi-layer tube while vacuum is applied to the mold, a pumping operation in which pressurized gas is pumped into tube space, an expanding operation in which the pressurized gas expands the multi-layer tube against an inner surface of the mold, an opening operation in which the mold is opened and a vessel is released, and a trimming operation in which excess material is trimmed from the vessel to establish a multi-layer container in accordance with the present disclosure as suggested in Fig. 13;
  • FIG. 2 is a diagrammatic view of the container-molding process of Fig. 2 showing that the container-molding process includes a series of operations which produce the multi-layer tube and form the multi-layer container;
  • Fig. 3 is a perspective and diagrammatic view of the co-extrusion system used to make the multi-layer tube showing that the co-extrusion system includes an outer-layer extruder configured to receive an outer-layer formulation and provide an outer-layer parison, an inner- layer extruder configured to receive an inner-layer formulation and provide an inner-layer parison, a core-layer extruder configured to receive a core-layer formulation and provide a core- layer parison, and a co-extrusion die coupled to each of the extruders to receive the associated parisons and configured to extrude the inner-layer, core-layer, and outer-layer parisons to establish the multi-layer tube;
  • the co-extrusion system includes an outer-layer extruder configured to receive an outer-layer formulation and provide an outer-layer parison, an inner- layer extruder configured to receive an inner-layer formulation and provide an inner-layer parison, a core-layer extruder configured to receive a core-layer formulation and provide a core-
  • Fig. 4 is a partial perspective view taken from below the co-extrusion die of the co-extrusion system showing that the co-extrusion die includes an annular aperture configured to extrude the multi-layer tube;
  • Fig. 5 is a view similar to Fig. 4 after co-extrusion of the multi-layer tube has begun with portions of the multi-layer tube broken away to reveal that the inner layer is spaced apart from the outer layer and that the core layer is located therebetween;
  • FIG. 6 is an enlarged partial perspective view of Fig. 1 showing that prior to the closing operation, the multi-layer tube is located between two mold halves and that a vacuum source coupled to the mold is turned off so that atmospheric pressure exists in a mold cavity formed between the two mold halves when the mold is in a closed position;
  • FIG. 7 is an enlarged partial perspective view of Fig. 1 showing that after the closing operation, the vacuum source is turned on and pressure inside the mold cavity decreases to establish a vacuum in the mold cavity which minimizes loss of cell structure in the core layer during the blowing and expanding operations;
  • Fig. 8A is a sectional view taken along line 8A-8A of Fig. 7 showing that prior to the blowing operation, the multi-layer tube has an outer tube surface which establishes a preform radius and an inner surface of the mold has a relatively greater mold radius;
  • Fig. 8B is a view similar to Fig. 8A taken along line 8B-8B of Fig. 1 showing that the multi-layer tube has expanded to engage the inner surface of the mold after the expanding operation is complete and that the vessel includes an outer container surface which establishes a relatively greater container radius which is about equal to the mold radius;
  • Fig. 9 is a view similar to Fig. 7 showing the mold and multi-layer tube after the inserting operation in which the blow needle is inserted through the mold and into the tube space of the multi-layer tube and that a pressurized source of gas is turned off so that a pressure in the space is about atmospheric;
  • Fig. 10 is sectional view taken along line 10-10 of Fig. 9 showing that prior to the blowing operation, the core layer of the multi-layer tube includes a plurality of expanded cells filled with gas which cause a density of the core layer to be minimized so that a density of the of the multi-layer container is also minimized;
  • Fig. 11 is view similar to Fig. 9 showing the mold and multi-layer tube during the expanding operation in which the source of pressurized gas has been turned on causing pressure in the tube space to increase to P BLOW which is above atmospheric pressure so that the multilayer tube expands outwardly toward the inner surface of the mold;
  • Fig. 12 is a view similar to Fig. 10 taken along line 12-12 of Fig. 11 showing that during the expanding operation, the plurality of expanded cells remain intact in the core layer so that the density of the vessel is minimized;
  • Fig. 13 is a perspective view of the multi-layer container formed from the container-molding process of Figs. 1 and 2 after the trimming operation has completed;
  • Fig. 14 is a sectional view taken along line 14-14 of Fig. 13 showing that the multi-layer container includes a side wall including the inner layer, the outer layer spaced apart from the inner layer, and a compressed core layer located therebetween and showing that some of the expanded cells have collapsed along the inner and outer layers to cause the compressed core layer to have a relatively greater density than the core layer of the multi-form tube;
  • Fig. 15 is a partial perspective view of the multi-layer container of Fig. 13 coupled to a top-load testing device undergoing top-load testing;
  • Fig. 16 is a photograph of the multi-layer container of Fig. 13 coupled to a rigidity testing device undergoing rigidity testing;
  • Fig. 17 is a perspective view of an unassembled density determination apparatus showing the components (clockwise starting in the upper left) gem holder, platform, suspension bracket, and suspension spacer.
  • Multi-layer container 10 is suggested in Fig. 1 and shown in Fig. 13.
  • Multi-layer container 10 is formed by a container-molding process 100 in accordance with the present disclosure as shown in Fig. 1 and suggested in Fig. 2.
  • Container-molding process 100 begins with extruding 102 a multi-layer tube 12 that includes a core layer 12B made from relatively low-density insulative cellular non-aromatic polymeric material.
  • Container-molding process 100 proceeds by molding multi-layer tube 12 into multilayer container 10 which may cause core layer 12B of multi-layer tube 12 to compress and establish a compressed core layer 10B included in multi-layer container 10.
  • compressed core layer 10B being made from relatively low-density insulative cellular non- aromatic polymeric material, a density of multi-layer container 10 is minimized while stack strength, rigidity, and top-load performance of multi-layer container 10 are maximized.
  • Container-molding process 100 begins with an extruding operation 102 in which multi-layer tube 12 is extruded from a co-extrusion system 16 as suggested in Fig. 1 and shown in Fig. 3.
  • Container- molding process 100 then proceeds to a closing operation 104 in which a mold 18 is closed around multi-layer tube 12 as shown in Fig. 1.
  • Container-molding process then moves onto an inserting operation 106 in which a blow needle 20 is inserted into a tube space 22 formed in multi-layer tube 12 while vacuum from a vacuum source 24 is applied to mold 18.
  • Container-molding process 100 then proceeds to a pumping operation 108 in which pressurized gas 26 is pumped into tube space 22 as suggested in Fig. 1.
  • Container-molding process 100 then moves on to simultaneous operations including a vacuuming operation 109 in which vacuum is applied to mold 18 and an expanding operation 110 in which pressurized gas 26 expands multi-layer tube 12 against an inner surface 28 of mold 18 and establishes a vessel 30.
  • An opening operation 112 then occurs in which mold 18 opens to reveal vessel 30.
  • a removing operation 114 occurs in which vessel 30 is separated from mold 18 and released from blow needle 20.
  • Container-molding process 100 then ends with a trimming operation 116 in which excess materials 62, 64 are trimmed from multi-layer container 10 to establish multi-layer container 10 as suggested in Fig. 1 and shown in Fig. 13.
  • Multi-layer container 10 is made during container-molding process 100 using multi-layer tube 12 as shown in Fig. 1.
  • Multi-layer tube 12 is provided during extruding operation 102 of container-molding process 100.
  • Extruding operation 102 is performed using co-extrusion system 16 as shown in Fig. 3.
  • Extruding operation 102 includes a preparing stage 102A in which various material formulations are provided to co-extrusion system 16, an extrusion stage 102B in which the various material formulations are processed by co-extrusion system 16 to provide associated parisons, and a co-extruding stage 102C in which the various parisons are extruded to provide multi-layer tube 12 as shown in Fig. 1 and suggested in Fig. 3.
  • Extruding operation 102 is performed on co-extrusion system 16 which includes an inner-layer extruder 32, an outer-layer extruder 34, a core-layer extruder 36, and a co- extrusion die 38 as shown in Fig. 3.
  • Inner-layer extruder 32 receives an inner-layer formulation 40 of a relatively high-density polymeric material and processes inner-layer formulation 40 to provide an inner-layer parison 42 to co-extrusion die 38 as shown in Fig. 3.
  • Outer-layer extruder 34 receives an outer-layer formulation 44 of a relatively high-density polymeric material and processes outer-layer formulation 44 to provide an outer-layer parison 46 to co- extrusion die 38 as shown in Fig. 3.
  • Core-layer extruder 36 receives a core-layer formulation 48 of a relatively low-density insulative cellular non-aromatic polymeric material and processes core-layer formulation 48 to provide a core-layer parison 50 to co-extrusion die 38 as shown in Fig. 3.
  • Co-extrusion die 38 receives the various parisons 42, 46, 50 and extrudes multi-layer tube 12 through an annular aperture 39 as suggested in Figs. 1 and 3 and shown in Figs. 4 and 5.
  • extruding operation 102 is shown forming multi-layer tube 12 having three layers, any number of layers may be formed during the extruding operation. Additional layers may include relatively low-density layers, tie layers, thermoplastic polyurethane (TPU), other olefins, combinations thereof, or any other suitable alternatives and combinations.
  • TPU thermoplastic polyurethane
  • Molding system 52 includes, for example, mold 18 formed to include a mold cavity 54 defined by inner surface 28 of mold 18, a vacuum system 56 configured to provide a vacuum pressure to mold cavity 54 during molding of multi-layer container 10, a blowing system 58 configured to provide pressurized gas 26 to tube space 22, and a trimming system 60 configured to remove excess materials 62, 64 from vessel 30 as shown in Fig. 1.
  • Container-molding process 100 proceeds to closing operation 104 after multilayer tube 12 has been established as shown in Figs. 1 and 2.
  • First and second mold halves 18A, 18B included in mold 18 begin in an opened position in which mold halves 18 A, 18B are spaced apart from one another as shown in Fig. 1.
  • mold halves 18A, 18B move toward one another to achieve a closed position in which multi-layer tube 12 is located in mold cavity 54 formed therebetween.
  • a vacuum source 66 included in vacuum system 56 remains off and pressure in mold cavity 54 remains at about atmospheric pressure as measured by a mold-cavity pressure gauge 68 as shown in Fig. 1.
  • container-molding process 100 proceeds to inserting operation 106 as shown in Figs. 1 and 2.
  • inserting operation 106 mold 18 moves away from co-extrusion die 38 and aligns with blow needle 20 included in blowing system 58.
  • Blow needle 20 then moves downwardly through mold 18 into tube space 22 included in multi-layer tube 12 as shown in Figs. 1 and 2.
  • vacuum source 66 is turned on causing pressure in mold cavity 54 to decrease to P VAC which is below atmospheric pressure. Vacuum is applied at a pressure in a range of about 5 mmHg to about 25 mmHg. In another example vacuum is applied at a pressure of about 20 mmHg.
  • P VAC is greater than the vacuum applied and less than atmospheric pressure.
  • P VAC may be in a range of about 5 inches Hg to about 20 inches Hg. In another example, P VAC is in a range of about 10 inches Hg to about 20 inches Hg. In still yet another example, P VAC is about 10 inches Hg.
  • a source 70 of pressurized gas 26 included in blowing system 58 may be communicated into tube space 22 to expand a size of multi-layer tube 12 in subsequent operations.
  • source 70 of pressurized gas 26 is turned off and pressure in tube space 22 is measured by a tube pressure gauge 72 to be at about atmospheric pressure (P ATM ).
  • Pressurized gas may be, for example, standard air, nitrogen, carbon dioxide, combinations thereof, or any other suitable alternative.
  • container-molding process 100 proceeds to pumping operation 108 as shown in Figs. 1 and 2.
  • source 70 of pressurized gas 26 is turned on and pressure inside tube space 22 increases to a relatively higher pressure (P BLOW) -
  • P BLOW is in a range of about 30 pounds per square inch and about 120 pounds per square inch.
  • P BLOW is in a range of about 10 pounds per square inch to about 130 pounds per square inch.
  • P BLOW is in a range of about 35 pounds per square inch to about 45 pounds per square inch.
  • P BLOW is about 40 pounds per square inch.
  • source 70 of pressurized gas 26 may be configured to deliver pressurized gas 26 at a temperature to tube space 22.
  • the temperature is in a range of about 35 degrees Fahrenheit to about 75 degrees Fahrenheit.
  • the temperature is in a range of about 40 degrees Fahrenheit to about 70 degrees Fahrenheit.
  • the temperature is in a range of about 50 degrees to about 75 degrees Fahrenheit.
  • the temperature is about room temperature.
  • the temperature is about 40 degrees Fahrenheit.
  • the temperature is about 50 degrees Fahrenheit.
  • container-molding process 100 proceeds to both vacuuming operation 109 and expanding operation 110 as shown in Figs. 1 and 2.
  • vacuuming operation 109 vacuum is applied to mold cavity 54.
  • expanding operation 110 commences.
  • pressurized gas 26 continues to flow through blow needle 20 causing multi-layer tube 12 to expand and engage inner surface 28 of mold 18 and fill mold cavity 54 as suggested in Fig. 1 and Fig. 11.
  • Expanding operation 110 is complete once multi-layer tube 12 has substantially the same shape as mold cavity 54.
  • vacuum source 66 remains on and pressure in mold cavity 54 remains below atmospheric pressure to minimize collapse and damage of expanded cells 69 included in core layer 12B of multi-layer tube 12 as shown in Fig. 12.
  • Pumping operation 108, vacuuming operation, and expanding operation 110 cause multi-layer tube 12 to expand from a pre-expansion shape as shown in Figs. 8A and 9 to a post-expansion shape shown in Figs. 1 and 8B which is substantially similar to a shape of vessel 30.
  • An outer tube surface 76 of multi-layer tube 12 has a pre-form radius 78 as shown in Fig. 8 A.
  • Inner surface 28 of mold 18 has a relatively greater mold radius 80 as shown in Fig. 8 A.
  • vessel 30 has an outer container surface 82 which has a relatively greater container radius 84. Relatively greater container radius 84 is about equal to relatively greater mold radius 80 after expanding operation 110 is complete.
  • a blow-up ratio for mold 18 and multi-layer tube 12 is calculated by dividing mold radius 80 by pre-form radius 78.
  • the blow-up ratio is in a range of about 100% to about 300%.
  • the blow-up ratio is in a range of about 150% to about 200%.
  • the blow-up ratio is about 200%. The blow-up ratio may be adjusted to suit various sizes of containers.
  • vessel 30 After expanding operation 110 is complete, vessel 30 is established. Vessel 30 includes multi-layer container 10 and excess material 62 coupled to an upper end of multi-layer container 10 and excess material 64 coupled to a lower end of multi-layer container 10.
  • Container-molding process 100 then proceeds to opening operation 112 as shown in Figs. 1 and 2.
  • opening operation 112 source 70 of pressurized gas 26 is turned off and mold 18 moves from the closed position to the opened position as shown in Fig. 1.
  • Vessel 30 is then ready for removal from mold 18 and while remaining coupled to blow needle 20 as suggested in Fig. 1.
  • Container-molding process 100 then proceeds to removing operation 114 in which vessel 30 is separated from mold 18 and released from blow needle 20.
  • source 70 of pressurized gas 26 briefly turns on blowing vessel 30 off of blow needle 20.
  • container-molding process 100 proceeds to trimming operation 116. During trimming operation 116, excess material 62, 64 is cut using one or more knives 86 or blades to provide multi-layer container 10 as shown in Fig. 1.
  • Molding system 52 is used in cooperation with a continuous extrusion process such as extruding operation 102.
  • molding system 52 may be a shuttle blow-molding machine.
  • mold 18 begins in the opened position and moves on a track toward co-extrusion die 38 to locate multi-layer tube 12 between mold halves 18 A, 18B. Mold 18 then moves to the closed position. Mold 18 then slides away from co-extrusion die 18 while another multi-layer tube 12 is extruded.
  • inserting operation 106, pumping operation 108, and expanding operation 110 are performed. Opening operation 112 and removing operations 114 are then performed which cause vessel 30 to be ejected from mold 18.
  • Mold 18 is now in the opened position ready to slide back toward co-extrusion die 30 and begin the process again.
  • One example molding machine 52 is a shuttle blow-molding machine available from Graham Engineering Corporation of York, Pennsylvania. In another example of a shuttle blow-molding machine, more than one mold may be used to minimize cycle time and increase an extrusion rate of co-extrusion system 16.
  • molding machine 52 may be a rotary blow molding machine.
  • a continuous multi-layer tube is extruded and a series of molds included in the rotary blow-molding machine rotate relative to the multi-layer tube. As molds approach co- extrusion die 38 forming the multi-layer tube 10, they begin to move from an opened
  • Container-molding process 100 has a cycle time defined as an amount of time between closing operation 104 and opening operation 112. This cycle time is defined the same way whether molding machine 52 is a shuttle blow-molding machine or a rotary extrusion blow- molding machine.
  • Multi-layer containers including core layer 12B made from relatively low- density insulative cellular non-aromatic polymeric material may have decreased cycle time due to reduced mass of the container resulting from the use of core-layer 12B.
  • the cycle time for container- molding process 100 and multi-layer container 10 on a shuttle blow-molding machine is in a range of about 5% to about 40% faster than molding operations and containers lacking a layer made from relatively low-density insulative cellular non-aromatic polymeric material.
  • cycle time may be in a range of about 5% to about 30% faster than molding operations and containers lacking a layer made from relatively low-density insulative cellular non-aromatic polymeric material.
  • the cycle time of container-molding process 100 and multi-layer container 10 was about 16 seconds.
  • Container-molding process 100 uses multi-layer tube 12 to establish multi-layer container 10 as shown, for example, in Figs. 1 and 13.
  • Multi-layer container 10 includes a floor 88, a sidewall 90, and neck 92 as shown in Fig. 13.
  • Sidewall 90 is relatively straight and vertical and provides outer container surface 82.
  • Floor 88 is coupled to a lower end of sidewall 90 and cooperates with sidewall 90 to define an interior product-storage region 94 therebetween.
  • Neck 92 is coupled to an opposite upper end of sidewall 90 and defines an open mouth 96 that is arranged to open into interior product-storage region 94.
  • Neck 92 has a neck radius 98 which is relatively smaller than container radius 84 as shown in Fig. 13.
  • Multi-layer container 10 was subjected to a series of performance tests which include drop testing, top load testing, rigidity testing, and metrology testing.
  • Drop testing determines a likelihood of container survival due to a drop or impact to the container.
  • Top load testing determines how much force a container can withstand before the container fails or necks in to form an hourglass shape.
  • Rigidity testing determines how resistant containers are to deformation.
  • Metrology testing determines dimensions of multi-layer container 10 in comparison to specifications for the container.
  • Multi-layer container 10 was subjected to drop testing according to one of the
  • the drop test may be performed according to the following procedure.
  • the container is filled with water and closed off with, for example, a lid.
  • the sample container is then held at about 73 degrees Fahrenheit (22.8 degrees Celsius) and about 50% relative humidity.
  • the filled, capped containers are then subjected to the following procedure: (a) the filled, capped container is located at about five feet above a hard surface such as concrete or tile; (b) the filled, capped container is then oriented such that a bottom of the filled, capped container is arranged to lie in a substantially parallel relation to the hard surface; (c) each of ten capped, filled containers are dropped; (d) upon impact, each filled, capped container is examined for any break or shattering of the wall that causes water to leak out of the bottle; and (d) the total number of bottles showing any sign of leakage after the drop test are counted as failures. Results for various different trial runs of multi-layer container 10 are shown below in Table. 1.
  • Instron tester 202 is used to determine top load performance as suggested in Fig. 15. Multi-layer containers 10 were tested until they failed or necked in to form an hourglass shape. Once failure or necking was observed, the value shown on Instron tester 202 was recorded. Table 2 shows the performance of several multi-layer containers including compressed core layer 10B tested vs. several high density polyethylene containers (excluding a core layer). Both types of containers had a total mass of about 56 grams.
  • FIG. 16 Various multi-layer containers 10 in accordance with the present disclosure were subjected to rigidity testing. Each multi-layer container was placed in a rigidity tester as shown in Fig. 16 and tested to determine rigidity as shown below in Table 3. Testing involves placing a multi-layer container in a rigidity tester 300 as shown in Fig. 16 in two orientations.
  • the rigidity tester includes a stationary cylindrical stop 302 on a left side and a movable anvil 304 and force gauge 306 on a right side.
  • the movable anvil is generally T-shaped as shown in Fig. 16. For each orientation, sidewall 90 of multi-layer container 10 is deformed about midway between floor 88 and neck 92 of multi-layer container 10.
  • Table 4 shows a neck diameter 204 measured at different points along a multi-layer container for several multi-layer containers along with the specified values and limits for each multi-layer container. The measurements were taken at 0 degrees (part line of the mold), 90 degrees (counter-clockwise from the part line), 45 degrees (counter-clockwise from the part line), 135 degrees (counter-clockwise from the part line), average neck diameter, and ovality of the neck. Ovality is the difference between highest and lowest neck diameter measurements.
  • Various multi-layer containers 10 were subjected to metrology measurements to determine accuracy and repeatability of container-molding process 100 to manufacture multilayer containers 10 to specification.
  • Table 5 shows a thread diameter 206 measured at different points along a multi-layer container for several multi-layer containers along with the specified values and limits for each multi-layer container. The measurements were taken at 0 degrees (part line of the mold), 90 degrees (counter-clockwise from the part line), 45 degrees (counter-clockwise from the part line), 135 degrees (counter-clockwise from the part line), average neck diameter, and ovality of the neck. Ovality is the difference between highest and lowest thread diameter measurements.
  • Various multi-layer containers 10 were subjected to metrology measurements to determine accuracy and repeatability of container-molding process 100 to manufacture multilayer containers 10 to specification.
  • Table 6 shows various measurements taken for several multi-layer containers along with the specified values and limits for each multi-layer container. The measurements taken were an Overall Height (OAH) of the container, an outside diameter of the sidewall taken at 0 degrees (part line of the mold) and 90 degrees (counterclockwise from the part line), an average outside diameter, ovality of the diameter, weight of the container, OFC.
  • OFC is an overflow capacity of multi-layer container 10 and measured in cubic centimeters (cc).
  • Various multi-layer containers 10 were subjected to metrology measurements to determine accuracy and repeatability of container-molding process 100 to manufacture multilayer containers 10 to specification.
  • Table 7 below shows various thicknesses for each inner, outer, and core layer for several multi-layer containers.
  • Table 8 shows various layer thicknesses as a percent of a total thickness for each inner, outer, and core layer and a layer distribution between solid (inner and outer layer) cellular (core layer) for several multi-layer containers.
  • a total solid phase distribution of inner and outer layers is targeted at about 12- 15% while a cellular phase distribution is targeted about 85-88% as suggested in Table 8 below.
  • Multi-layer container 10 is made using container- molding process 100 which begins with an extruding operation 102 as shown in Figs. 1-3.
  • Extruding operation 102 includes several stages that each comprise several operations which cooperate to provide multi-layer tube 12.
  • extruding operation 102 includes a preparing stage 102A in which various material formulations are prepared and provided to each associated extruder to provide the associated layer of multi-layer tube 12.
  • Extruding operation 102 further includes an extrusion stage 102B in which the various formulations are processed by associated extruders to provide associated parisons which are communicated to co-extrusion die 38 as shown in Figs. 1 and 3.
  • extruding operation 102 ends with a co-extruding stage 102C in which the various parisons are aligned and co-extruded together to establish multi-layer tube 12.
  • Preparing stage 102 A of extruding operation 102 further includes a second preparing operation 102A2.
  • outer-layer formulation 44 is prepared and provided to outer-layer extruder 34 as shown in Fig. 3.
  • outer-layer formulation 44 comprises at least one polymeric material.
  • the polymeric material may include one or more resins.
  • inner-layer formulation 40 includes a relatively high-density polymeric material.
  • inner-layer formulation 40 comprises relatively high-density polymeric material.
  • inner-layer formulation 40 is FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation).
  • core-layer formulation 48 used to produce the insulative cellular non-aromatic polymeric material includes at least one polymeric material.
  • the polymeric material may include one or more base resins.
  • the base resin is High Density Polyethylene (HDPE).
  • the base resin is a unimodal HDPE.
  • the base resin is unimodal, high-melt strength HDPE.
  • the base resin is unimodal, high-melt strength HDPE such as DOW®
  • DOWLEXTM IP 41 HDPE available from The Dow Chemical Company that has been electron beam modified to provide long chain branching and a melt index of about 0.25 g/10 min.
  • Long chain branching refers to the presence of polymer side chains (branches) that have a length that is comparable or greater than a length of the backbone to which the polymer side chains are coupled to. Long chain branching creates viscoelastic chain
  • the strain hardening phenomenon may be observed through two analytical methods.
  • the second analytical method used to observe the presence of long chain branching is evaluating melt strength data as tested per ISO 16790 which is incorporated by reference herein in its entirety.
  • An amount of melt strength is known to be directly related to the presence of long chain branching when compared to similar virgin polymers lacking long chain branching.
  • Borealis DAPLOYTM WB140HMS Polypropylene (PP) (available from Borealis AG) is compared to other polymers having similar molecular weight, polydispersity index, and other physical characteristics.
  • the DAPLOYTM WB140HMS PP has a melt strength which exceeds about 36 centi-Newton while other similar PP resins lacking long chain branching have a melt strength of less than about 10 centi-Newton.
  • Suitable physical nucleating agents have desirable particle size, aspect ratio, and top-cut properties. Examples include, but are not limited to, talc, CaC0 3 , mica, and mixtures of at least two of the foregoing.
  • talc talc
  • CaC0 3 CaC0 3
  • mica talc
  • One representative example is Heritage Plastics HT6000 Linear Low Density Polyethylene (LLDPE) Based Talc Concentrate.
  • Suitable chemical nucleating agents decompose to create cells in the molten formulation when a chemical reaction temperature is reached. These small cells act as nucleation sites for larger cell growth from a physical or other type of blowing agent.
  • the chemical nucleating agent is citric acid or a citric acid-based material.
  • HYDROCEROLTM CF-40E available from Clariant Corporation, which contains citric acid and a crystal nucleating agent.
  • a core-layer formulation can include a nucleating agent.
  • the amount of a nucleating agent may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a nucleating agent and be one of the following values: about 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 5%, 10%, and 15% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a nucleating agent in the formulation to fall within one of many different ranges.
  • the range of a nucleating agent is one of the following ranges: about 0.1% to 5%, 0.25% to 5%, 0.5% to 5%, 0.75% to 5%, 1% to 5%, 1.5% to 5%, 2% to 5%, 2.5% to 5%, 3% to 5%, 3.5% to 5%, 4% to 5%, and 4.5% to 5% of the total formulation by weight percentage.
  • ranges about 0.1% to 5%, 0.25% to 5%, 0.5% to 5%, 0.75% to 5%, 1% to 5%, 1.5% to 5%, 2% to 5%, 2.5% to 5%, 3% to 5%, 3.5% to 5%, 4% to 5%, and 4.5% to 5% of the total formulation by weight percentage.
  • Chemical blowing agents are materials that degrade or react to produce a gas.
  • chemical blowing agents may be selected from the group consisting of azodicarbonamide; azodiisobutyro-nitrile; benzenesulfonhydrazide; 4,4- oxybenzene sulfonylsemicarbazide; p-toluene sulfonyl semi-carbazide; barium
  • dichlorotetrafluoroethane chloroheptafluoropropane; dichlorohexafluoropropane; methanol; ethanol; n-propanol; isopropanol; sodium bicarbonate; sodium carbonate; ammonium
  • bicarbonate ammonium carbonate; ammonium nitrite; N,N'-dimethyl-N,N'- dinitrosoterephthalamide; ⁇ , ⁇ '-dinitrosopentamethylene tetramine; azodicarbonamide; azobisisobutylonitrile; azocyclohexylnitrile; azodiaminobenzene; bariumazodicarboxylate;
  • benzene sulfonyl hydrazide toluene sulfonyl hydrazide; p,p'-oxybis(benzene sulfonyl hydrazide); diphenyl sulfone-3,3'-disulfonyl hydrazide; calcium azide; 4,4'-diphenyl disulfonyl azide; p-toluene sulfonyl azide, and combinations thereof.
  • the chemical blowing agent may be introduced into the material formulation that is added to the hopper.
  • N 2 nitrogen
  • the N 2 is pumped into the molten formulation via a port in the extruder as a supercritical fluid.
  • the molten material with the N 2 in suspension then exits the extruder via a die where a pressure drop occurs.
  • N 2 moves out of suspension toward the nucleation sites where cells grow. Excess gas blows off after extrusion with the remaining gas trapped in the cells formed in the extrudate.
  • Other suitable examples of physical blowing agents include, but are not limited to, carbon dioxide (C0 2 ), helium, argon, air, pentane, butane, or other alkane mixtures of the foregoing and the like.
  • a physical blowing agent may be introduced at a rate of about 0.02 pounds per hour to about 0.15 pounds per hour. In still yet another illustrative example, the physical blowing agent may be introduced at a rate of about 0.05 pounds per hours to about 0.15 pounds per hour.
  • At least one slip agent may be any slip agent.
  • Slip agent also known as a process aid
  • slip agent is a term used to describe a general class of materials which are added to the formulation and provide surface lubrication to the polymer during and after conversion. Slip agents may also reduce or eliminate die drool.
  • Representative examples of slip agent materials include amides of fats or fatty acids, such as, but not limited to, erucamide and oleamide. In one exemplary aspect, amides from oleyl (single unsaturated C-18) through erucyl (C-22 single unsaturated) may be used.
  • Other representative examples of slip agent materials include low molecular weight amides and fluoroelastomers. Combinations of two or more slip agents can be used. Slip agents may be provided in a master batch pellet form and blended with the resin formulation.
  • a suitable slip agent is Ampacet 102823 Process Aid PE MB LLDPE.
  • a core-layer formulation can include a slip agent.
  • the amount of a slip agent may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a slip agent and be one of the following values: about 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.25%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, and 3% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a slip agent in the formulation to fall within one of many different ranges.
  • the range of a slip agent is one of the following ranges: about 0% to 3%, 0.1% to 3%, 0.25% to 3%, 0.5% to 3%, 1% to 3%, 1.25% to 3%, 1.5% to 3%, 1.75% to 3%, 2% to 3%, 2.25% to 3%, and 2.5% to 3% of the total formulation by weight percentage.
  • the range of a slip agent is one of the following ranges: about 0% to 2.5%, 0% to 2%, 0% to 1.75%, 0% to 1.5%, 0% to 1.25%, 0% to 1%, 0% to 0.75%, 0% to 0.5%, and 0.1% to 2.5% of the total formulation by weight percentage.
  • the range of a slip agent is one of the following ranges: about 0.1% to 2.5%, 0.1% to 2%, 0.1% to 1.75%, 0.1% to 1.5%, 0.1% to 1.25%, 0.1% to 1%, 0.1% to 0.75%, and 0.1% to 0.5% of the total formulation by weight percentage.
  • an impact modifier may be incorporated into the formulation to minimize fracturing of the insulative cellular non-aromatic polymeric material when subjected to an impact such as a drop test.
  • a suitable impact modifier is DOW® AFFINITYTM PL 1880G polyolefin plastomer.
  • a colorant can be about 0% to about 4% (w/w), about 0.1% to about 4%, about 0.25% to about 4%, about 0.5% to about 4%, about 0.75% to about 4%, about 1.0% to about 4%, about 1.25% to about 4%, about 1.5% to about 4%, about 1.75% to about 4%, about 2.0% to about 4%, about 2.25% to about 4%, about 2.5% to about 4%, about 3% to about 4%, about 0% to about 3.0%, about 0% to about 2.5%, about 0% to about 2.25%, about 0% to about 2.0%, about 0% to about 1.75%, about 0% to about 1.5%, about 0% to about 1.25%, about 0% to about 1.0%, about 0% to about 0.75%, about 0% to about 0.5%, about 0.1% to about 3.5%, about 0.1% to about 3.0%, about 0.1% to about 2.5%, about 0.1% to about 2.25%, about 0.1% to about 2.0%, about 0.1%
  • a core-layer formulation can include a colorant.
  • the amount of a colorant may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a colorant and be one of the following values: about 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.25%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, 3%, and 4% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a slip agent in the formulation to fall within one of many different ranges.
  • the range of a colorant is one of the following ranges: about 0% to 4%, 0.1% to 4%, 0.25% to 4%, 0.5% to 4%, 1% to 4%, 1.25% to 4%, 1.5% to 4%, 1.75% to 4%, 2% to 4%, 2.25% to 4%, 2.5% to 4%, and 3% to 4% of the total formulation by weight percentage.
  • the range of a colorant is one of the following ranges: about 0% to 3%, 0% to 2.5%, about 0% to 2.25%, 0% to 2%, 0% to 1.75%, 0% to 1.5%, 0% to 1.25%, 0% to 1%, 0% to 0.75%, and 0% to 0.5% of the total formulation by weight percentage.
  • the range of a slip agent is one of the following ranges: about 0.1% to 3.5%, 0.1% to 3.0%, 0.1% to 2.5%, 0.1% to 2.25%, 0.1% to 2%, 0.1% to 1.75%, 0.1% to 1.5%, 0.1% to 1.25%, 0.1% to 1%, 0.1% to 0.75%, and 0.1% to 0.5% of the total formulation by weight percentage.
  • ranges about 0.1% to 3.5%, 0.1% to 3.0%, 0.1% to 2.5%, 0.1% to 2.25%, 0.1% to 2%, 0.1% to 1.75%, 0.1% to 1.5%, 0.1% to 1.25%, 0.1% to 1%, 0.1% to 0.75%, and 0.1% to 0.5% of the total formulation by weight percentage.
  • step (b) the inner parison core parison, and outer parison from step (a) are aligned such that the core parison is located between the inner parison and the outer parison and the aligned parisons are then co-extruded to form the multilayer tube.
  • the outer and inner parisons each comprise a high density polymeric material.
  • the high-density polymeric material is high density polyethylene or polypropylene.
  • the polypropylene used in either of the skin layers is a high stiffness polypropylene. More suitably, the polypropylene used in either of the skin layers is a high impact polypropylene. Even more suitably, the polypropylene used in either of the skin layers is DOW® D 207.03 developmental performance polypropylene resin or DOW® DC 7067.00 polypropylene impact copolymer. Reference is hereby made to U.S. Patent Application Serial No. 14/468,789, filed August 26, 2014 and titled POLYMERIC MATERIAL FOR
  • polypropylene resin and/or DOW® DC 7067.00 polypropylene impact copolymer are examples of polypropylene resin and/or DOW® DC 7067.00 polypropylene impact copolymer.
  • the polyethylene used in either of the inner and outer parisons is a high density ethylene hexane- 1 copolymer.
  • the high density polyethylene is a HDPE hexene copolymer.
  • the high density polyethylene is FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics
  • the polyethylene used in either of the inner and outer parisons may be Chevron Phillips MARLEX® HHM 5502 BN.
  • one or both of the inner and outer layers comprise a high- density polymeric material as hereinbefore defined and a colorant.
  • one or both of the inner and outer layers may comprise 95 - 99.9% (w/w) of a high-density polymeric material as hereinbefore defined and 0.1 to 5% (w/w) a colorant.
  • one or both of the inner and outer layers may comprise 97 - 99.9% (w/w) of a high-density polymeric material as hereinbefore defined and 0.1 to 3% (w/w) a colorant.
  • one or both of the inner and outer layers may comprise 98 - 99.5% (w/w) of a high-density polymeric material as hereinbefore defined and 0.5 to 2% (w/w) a colorant.
  • the relatively high-density polymeric material may be FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation) and the colorant may be COLORTECH® 11933-19 Titanium Oxide Colorant (available from COLORTECH® a PPM Company).
  • inner-layer formulation and outer-layer formulation may be the same. In other examples, inner-layer formulation and outer-layer formulation may be different.
  • the core formulation is suitably as defined hereinbefore.
  • the core formulation comprises:
  • HDPE high density polyethylene
  • nucleating agent as defined herein;
  • the core formulation comprises:
  • HDPE high density polyethylene
  • the core formulation comprises:
  • HDPE high density polyethylene
  • step (d) the expansion of the multilayer tube is achieved by blow molding the multi-layer tube using techniques known in the art.
  • a multilayer vessel obtainable, obtained, or directly obtained by a process defined herein.
  • the core parison comprises an insulative cellular non-aromatic polymeric material.
  • a method of producing a multilayer container comprising:
  • molding the multilayer tube to form a multilayer container in a molding system comprising a mold, a vacuum system providing a vacuum pressure to a mold cavity of the mold during molding, a blowing system providing pressurized gas to tube space, and a trimming system removing excess material from the container following the molding.
  • Clause 3 The method of any other clause, further comprising the step of applying a vacuum in a range of about 5 millimeters Hg to about 25 millimeters Hg to the mold cavity during the expanding step whereby the outer parison engages with the inner surface of the mold.
  • Clause 6. The method of any other clause, wherein the pressurized gas has a pressure in a range of about 30 pounds per square inch to about 50 pounds per square inch.
  • Clause 7. The method of any other clause, wherein the pressurized gas has a pressure of about 40 pounds per square inch.
  • Clause 8 The method of any other clause, wherein the expanding step includes inserting a blow needle into the interior region of the multi-layer tube and pumping pressurized gas into interior region at a temperature up to about 200 degrees Fahrenheit.
  • Clause 14 The method of any other clause, wherein the multi-layer container has an average collapse force of in a range of about 50 pounds-Force to about 400 pounds-Force.
  • Clause 32 The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 0° F to about 200 0 F.
  • Clause 33 The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 30° F to about 80 0 F.
  • Clause 34 The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 40° F to about 50 0 F.
  • Clause 36 The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 50° F.
  • Clause 37 The method of any other clause, wherein the pressurized gas is delivered at a temperature of about room temperature.
  • Clause 50 The method of any other clause, wherein the inner-layer formulation further comprises a colorant.
  • Clause 55 The method of any other clause, further comprising extruding a core-layer formulation to form the core parison, wherein the core-layer formulation comprises a high-density polymeric material.
  • nucleating agent is about 0.1% to 15% (w/w) of the core-layer formulation.
  • nucleating agent is a chemical nucleating agent, a physical nucleating agent, or both a chemical nucleating agent and a physical nucleating agent.
  • Clause 70 The method of any other clause, wherein the physical nucleating agent is about 0% to 7% (w/w) of the core-layer formulation.
  • blowing agent is citric acid or a citric acid-based material.
  • Clause 76 The method of any other clause, wherein the chemical blowing agent is a citric acid and a crystal nucleating agent.
  • benzenesulfonhydrazide 4,4-oxybenzene sulfonylsemicarbazide; p-toluene sulfonyl semi- carbazide; barium azodicarboxylate; N,N'-dimethyl-N,N'-dinitrosoterephthalamide;
  • trihydrazino triazine methane; ethane; propane; n-butane; isobutane; n-pentane; isopentane; neopentane; methyl fluoride; perfluoromethane; ethyl fluoride; 1,1-difluoroethane; 1,1,1- trifluoroethane; 1,1,1,2-tetrafluoro-ethane; pentafluoroethane; perfluoroethane; 2,2- difluoropropane; 1,1,1-trifluoropropane; perfluoropropane; perfluorobutane;
  • perfluorocyclobutane methyl chloride; methylene chloride; ethyl chloride; 1,1,1- trichloroethane; 1,1-dichloro-l-fluoroethane; 1-chloro- 1,1-difluoroethane; l,l-dichloro-2,2,2- trifluoroethane; 1 -chloro- 1 ,2,2,2-tetrafluoroethane; trichloromonofluoromethane;
  • dichlorodifluoromethane trichlorotrifluoroethane ; dichlorotetrafluoroethane ; chloroheptafluoropropane; dichlorohexafluoropropane; methanol; ethanol; n-propanol;
  • azocyclohexylnitrile azodiaminobenzene; bariumazodicarboxylate; benzene sulfonyl hydrazide; toluene sulfonyl hydrazide; p,p'-oxybis(benzene sulfonyl hydrazide); diphenyl sulfone-3,3'- disulfonyl hydrazide; calcium azide; 4,4' -diphenyl disulfonyl azide; and p-toluene sulfonyl azide.
  • Clause 78 The method of any other clause, wherein the core-layer formulation further comprises a physical blowing agent.
  • Clause 88 The method of any other clause, wherein the colorant is about 0% to 4% (w/w) of the core-layer formulation.
  • Clause 89 The method of any other clause, wherein the multilayer tube further comprises an additional layer selected from the group consisting of an oxygen barrier layer, an oxygen scavenging layer, a UV barrier layer, a tie layer, an additional structural layer, and combinations thereof.
  • Outer-layer formulation 44 comprises about 99% FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer and about 1% COLORTECH® 11933-19.
  • HB5502F HDPE hexene copolymer which was used as polyethylene base resin.
  • the polyethylene base resin was used in various percentages from about 97.95% to about 100% of the formulation. In some examples, the polyethylene base resin was blended with
  • HYDROCEROL® CF 40E as a nucleating agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent, and N2 as a blowing agent.
  • the blowing agent was used at levels between about 0.05 lbs/hr to about 0.15 lbs/hour.
  • COLORTECH® 11933-19 was added as a colorant in some examples.
  • Table 9 The various formulations and resulting multi-layer tube densities are shown below in Table 9.
  • the apparatus also included a thermometer to measure the suspension liquid temperature.
  • a suspension liquid is a fluid with a density lower than that of the sample to be measured.
  • the sample must sink in the suspension fluid to determine the sample density.
  • a Mettler AT400 balance (Mettler- Toledo LLC, Columbus, OH) was also used.
  • the density of a limestone-filled HDPE bottle was measured. After taring the balance to zero, the dry solid sample was weighed after placing it in the cup of the Mettler balance. The dry weight was 0.3833 g. After weighing the dry sample and before removing the sample from the cup, the balance was tared again. The sample was removed from the cup and placed on the gem holder in the suspension fluid. The sample was weighed providing the weight with a negative number (-0.3287 g). The number was converted to its absolute value (0.3287 g); the positive value is the sample buoyancy. The sample density was calculated by multiplying the dry weight (0.3833 g) by the suspension fluid density (0.8808 g/cc) and dividing by the sample buoyancy (0.3287 g), which equaled 1.0272 g/cc.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • core-formulation 48 comprised Versalite (A) or Versalite (B).
  • A Versalite
  • B Versalite
  • LLDPE comprised DOW® DOWLEXTM 2045G LLDPE (available from The Dow Chemical Company), electron beam modified to have long-chain branching and a melt index of about 0.2 or 0.13 g/lOmin.
  • the polyethylene base resin was blended with
  • HYDROCEROL® CF 40E as a chemical blowing agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent.
  • N 2 was used as a blowing agent.
  • the blowing agent was used at levels between about 0.02 lbs/hr to about 0.15 lbs/hour.
  • the molding machine 52 was a rotary extrusion blow-molding machine available from Wilmington Machinery of Wilmington, North Carolina. The RPM speed of this machine was at levels between about 5 RPM to about 75 RPM.
  • the various formulations are shown below in Table 10.
  • the blowing agent, N 2 was injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent.
  • the resulting expanded formulation was then extruded through a die head to establish a core-layer parison.
  • the core-layer parison was molded to form a container according to the present disclosure.
  • Containers formed according to Table 10 were subjected to a series of
  • Table 11 Parison densities, container densities, weights, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 3.
  • Core layer 48 comprised FORMOSA PLASTICS® FORMOLENE® HB5502F
  • HDPE hexene copolymer as a polyethylene base resin.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent, Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent.
  • N2 was used as a blowing agent. The percentages were about:
  • a mold was closed around the tube and a blow needle was inserted into a space formed in the tube. During inserting the needle, the mold moved away from the die head. In some examples, vacuum was applied to the mold and in others no vacuum was applied to the mold. Vacuum caused the pressure to decrease to P VAC , which is between about 0 inches Hg and about 29 inches Hg. Pressurized gas, in some examples air, was pumped into a space formed in the tube to cause the tube to expand and take on the shape of the mold. In the next step, the mold was opened to reveal a container.
  • Cycle time is defined as an amount of time between closing the mold around the tube and opening the mold to reveal a container.
  • cycle time was varied between 14 and 18 seconds.
  • gas pressure varied between about 40 psi and about 60 psi.
  • pressurized gas was about room temperature.
  • Drop testing determines a likelihood of container survival due to a drop or impact to the container.
  • Containers were subjected to a drop testing procedure based on ASTM D2463 (Standard Test Method for Drop Impact Resistance of Blow-Molded Thermoplastic Containers), which is incorporated by reference herein in its entirety.
  • the drop test was performed according to the following procedure.
  • a bucket was filled with tap water.
  • the water in the bucket was allowed to condition for at least 24 hours at about room temperature and about 75% relative humidity.
  • the container was filled with water from the bucket and closed off with, for example, a lid.
  • the filled, capped containers were then subjected to the following procedure: (a) the filled, capped container was located at about five feet above a hard surface such as concrete or tile; (b) the filled, capped container was then oriented such that a bottom of the filled, capped container was arranged to lie in a substantially parallel relation to the hard surface; (c) each of ten capped, filled containers were dropped; (d) upon impact, each filled, capped container was examined for any break or shattering of the wall that causes water to leak out of the bottle; and (d) the total number of bottles showing any sign of leakage after the drop test were counted as failures.
  • Top load testing determines how much force a container can withstand before the container fails or necks in to form an hourglass shape.
  • Various containers 10 were subjected to top load testing.
  • An Instron tester such as and generally consistent with an Instron Series 5500 Load Frame, may be used to determine top load performance as suggested in Fig. 15.
  • the top load test was generally performed according to the following procedure.
  • a container was placed on a flat surface such that the floor of the container was arranged to lie in a substantially parallel relation to the flat surface.
  • a crosshead of the Instrom tester applied a compressive force to the top of the neck of the container.
  • a load transducer mounted in series with the container, measured the applied load.
  • Containers 10 were tested until they failed or necked in to form an hourglass shape. Once failure or necking was observed, the value shown on Instron tester was recorded.
  • Containers formed according to Table 12 were subjected to a series of
  • measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force performance measurements, and drop testing. The results are shown below in Table 13.
  • Table 13 Parison densities, bottle densities, weight, top load performance, bottle sidewall thicknesses, and drop test results of different insulative cellular non-aromatic polymeric material formulations of Example 5.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin.
  • EQUISTAR® ALATHON® H5520 HDPE copolymer (available from Lyondell Chemical Company), electron beam modified to have long-chain branching and a melt index of about 0.75 g/lOmin, was used as a second material of the polyethylene base resin.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent.
  • N 2 was used as a blowing agent.
  • the blowing agent was used at levels between about 0.03 lbs/hr to about 0.11 lbs/hour.
  • Containers formed according to Table 12 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, and top load force performance measurements. The results are shown below in Table 13.
  • Table 15 Parison densities, bottle densities, weight, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 9.
  • Core-layer formulation 48 comprises FORMOSA PLASTICS® FORMOLENE®
  • the blowing agent, N 2 is injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent.
  • the resulting expanded formulation is then extruded through a die head to establish a core-layer parison.
  • the tube is molded to form a container according to the present disclosure.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • Table 18 Parison densities, bottle densities, weights, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 12.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • a mold was closed around the tube and a blow needle was inserted into a space formed in the tube. During inserting the needle, the mold moved away from the die head.
  • Vacuum was applied to the mold and caused the pressure to decrease to P VAC , which is between about 0 inches Hg and about 29 inches Hg.
  • Pressurized gas in some examples air, was pumped into a space formed in the tube to cause the tube to expand and take on the shape of the mold.
  • the pressurized gas in this example was about 40 psi and about room temperature.
  • the mold was opened to reveal a container.
  • Cycle time is defined as an amount of time between closing the mold around the tube and opening the mold to reveal a container.
  • the cycle time in this example was between 14 and 16 second. In one example, cycle time was 15 seconds.
  • Thickness for Formulations of Example 14 [00299] Containers formed according to Table 19 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force performance measurements, and drop testing. The results are shown below in Table 20.
  • Table 20 Parison densities, bottle Densities, weight, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 14.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • the FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer comprises various amounts of virgin and second pass regrind material.
  • Second pass regrind material may be, for example, material prepared previously in Table 17 which included first pass regrind.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 was used as a blowing agent. The percentages were about:
  • the HDPE and nucleating agents were added to an extruder hopper and blended to provide a formulation.
  • the formulation was then heated in the extruder to form a molten formulation.
  • the blowing agent was then added to the molten formulation at a rate of about:
  • Table 21 Virgin/second pass regrind percentages and molding parameters used to form containers of Example 16. Table 17 formulations were run through Table 21.
  • Containers formed according to Table 21 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force measurements, and drop testing. The results are shown below in Table 22.
  • Table 22 Parison densities, bottle densities, weight, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 16.
  • HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin.
  • the FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer comprises various amounts of virgin and second pass regrind material.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 was used as a blowing agent. The percentages were about:
  • the HDPE and nucleating agents were added to an extruder hopper and blended to provide a formulation.
  • the formulation was then heated in the extruder to form a molten formulation.
  • the blowing agent was then added to the molten formulation at a rate of about:
  • Containers were prepared according to the present disclosure.
  • the molding machine 52 was a rotary extrusion blow-molding machine available from Wilmington
  • Containers were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force measurements, and drop testing. The results are shown below in Table 23.
  • Rigidity testing determines how resistant containers are to deformation.
  • Various multi-layer containers 10 in accordance with the present disclosure were subjected to rigidity testing. Each multi-layer container was placed in a rigidity tester as shown in Fig. 16 and tested to determine rigidity as shown below in Table 3. Testing involved placing a multi-layer container in a rigidity tester 300 as shown in Fig. 16 in two orientations.
  • the rigidity tester included a stationary cylindrical stop 302 on a left side and a movable anvil 304 and force gauge 306 on a right side.
  • the movable anvil was generally T-shaped as shown in Fig. 16. For each orientation, sidewall 90 of multi-layer container 10 was deformed about midway between floor 88 and neck 92 of multi-layer container 10.
  • HDPE available from Chevron Phillips Chemical Company
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent.
  • N 2 was used as a blowing agent.
  • DOE 1-1 20% 99.6% 0.10% 0.30% 75% 5% 20% 100% 0%
  • Thicknesses of insulative cellular non-aromatic polymeric material formulations of Example 23 were obtained by insulative cellular non-aromatic polymeric material formulations of Example 23.
  • DOE 1-1 11.35 17.1 0.710 0.039 0.025 0.062
  • DOE 1-4 11.4 17.7 0.644 0.036 0.025 0.064

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)

Abstract

La présente invention concerne un récipient, qui est conçu pour maintenir un produit dans une région intérieure formée dans le récipient. Le récipient comprend une couche intérieure conçue pour définir la région intérieure, et une couche extérieure. Le récipient est formé à l'aide d'un processus de moulage par soufflage dans lequel une paraison à couches multiples est moulée par soufflage pour former le récipient. La paraison à couches multiples est formée lors d'un processus d'extrusion dans lequel un certain nombre d'extrudeuses sont conçues pour réaliser une co-extrusion associée.
EP14838960.4A 2013-08-30 2014-09-02 Récipient et son procédé de fabrication Withdrawn EP3038810A4 (fr)

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US10576679B2 (en) 2020-03-03
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US9969116B2 (en) 2018-05-15
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